JP6210815B2 - Compound containing sulfonic acid (salt) group and amino group and method for producing the same - Google Patents

Description

  The present invention relates to a compound containing a sulfonic acid (salt) group and an amino group and a method for producing the same. More specifically, the present invention relates to a compound containing a sulfonic acid (salt) group and an amino group that can be used as a raw material for a polymer useful as a water treatment agent and the like, and a method for producing the same.

Conventionally, polymers containing sulfonic acid (salt) groups have been used in a wide range of fields such as water treatment agents and dispersants (for example, Patent Document 1).
Patent Document 2 discloses (i) a structural unit (a) derived from a polyalkylene glycol monomer (A), and (ii) a structural unit (b) derived from a carboxyl group-containing monomer (B). ), And the polyalkylene glycol-based polymer, wherein the polyalkylene glycol-based monomer (A) is represented by the following general formula (R-1);

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. Where n is the average number of moles added of the oxyalkylene group and represents a number from 1 to 300. X and Y are a hydroxyl group, a structure represented by the following general formula (R-2), and a general formula (R -3) represents a structure represented by (wherein either one of X and Y represents a hydroxyl group, and the other one represents a structure represented by the following general formula (R-2) or Represents a structure represented by the formula (R-3)).

(In the general formula (R-2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The general formula (R -2) and (R-3), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group).
The polyalkylene glycol polymer has a structure represented by the formula (1) with respect to 100 mass% of the total amount of structural units derived from all monomers forming the polymer: A polyalkylene glycol polymer containing 99% by mass and containing 1 to 99% by mass of the structural unit (b) is disclosed.
Patent Document 2 discloses that the polyalkylene glycol-based polymer exhibits good gel resistance.

  On the other hand, Patent Document 3 discloses an amino group-containing monomer represented by the following general formula (R-4).

In the general formula (R-4), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ are the same. Or differently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, Y ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, and n represents an oxyalkylene group (—Y ₁ —O— ) Represents the average number of moles added, and represents a number from 1 to 300.
Patent Document 3 discloses that the amino group-containing monomer represented by the general formula (R-4) has excellent copolymerizability with various nonionic monomers and cationic monomers. Yes.

JP 2002-3536 A JP 2012-57096 A JP 2012-56911 A

The polyalkylene glycol-based polymer of Patent Document 2 shows a very good gelation resistance even under high hardness, and is therefore a raw material although it has been proposed to be used as an additive for water treatment agents. The monomer represented by the general formula (R-1) contains many impurities, and these impurities should be removed by purification of the monomer represented by the general formula (R-1). Therefore, when the polyalkylene glycol polymer is blended with a water treatment agent, a large amount of the impurities or impurities resulting therefrom are blended.
The impurities do not contribute to the performance of the water treatment agent at all, and it is preferable to reduce the impurities as much as possible from the viewpoint of the stability of the water treatment agent and the stable operation of the cooling water system.
Specifically, in the monomer represented by the general formula (R-1), a raw material such as sodium bisulfite is added to a double bond of a compound represented by the following general formula (1) which is an intermediate. The bisulfite was added to both the double bond and the glycidyl group of the compound represented by the following general formula (2) and / or the compound represented by the following general formula (1). Contains a large amount of compounds and the like. Since these compounds do not have a polymerizable double bond, they will continue to exist as impurities after polymerization.

In the general formula (1), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. Or represents a CH ₃ group, and n is the average number of added moles of the oxyalkylene group and represents a number of 1 to 300.

In the general formula (2), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. Or represents a CH ₃ group, n is an average addition mole number of the oxyalkylene group and represents a number of 1 to 300, and M represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.

  The present invention has been made in view of the above-described situation, and it is possible to set the content of a non-polymerizable compound such as the compound represented by the general formula (2) to be small, for example, water treatment It aims at providing the compound containing the sulfonic acid group and amino group which can be used suitably as a raw material of the polymer for agents.

The present inventor has made various studies in order to achieve the above object, and arrived at the present invention.
That is, the compound containing a sulfonic acid (salt) group and an amino group of the present invention is a compound containing a sulfonic acid (salt) group and an amino group represented by the following general formula (3).

In the general formula (3), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. Or represents a CH ₃ group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n is an average addition mole number of an oxyalkylene group, 300 represents a number, m represents a number of 0 to 10, and SO ₃ ⁻ M ⁺ represents a sulfonic acid (salt) group (where M ⁺ represents a monoatomic ion or a polyvalent ion having a monovalent positive charge). Represents atomic ions).

Another aspect of the present invention provides a method for producing a compound containing a sulfonic acid (salt) group and an amino group. That is, the method for producing a compound containing a sulfonic acid (salt) group and an amino group of the present invention,
A sulfonic acid (salt) group and an amino group, comprising a step of reacting a compound represented by the following general formula (1-1) or (1-2) with a compound represented by the following general formula (4): It is a manufacturing method of the compound containing this.

In the general formulas (1-1) and (1-2), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, and R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group, or a single bond. R ₃ represents a hydrogen atom or a CH ₃ group, n represents the average number of moles added of the oxyalkylene group, and represents a number of 0 to 300. In general formula (1-2), X represents a halogen atom.

In General Formula (4), R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, m represents a number from 0 to 10, and SO ₃ ⁻ M ⁺ represents Represents a sulfonic acid (salt) group (where M ⁺ represents a monoatomic ion or polyatomic ion having a monovalent positive charge).

Since the compound containing a sulfonic acid (salt) group and an amino group of the present invention does not require the use of a bisulfite such as sodium bisulfite as a production raw material, the content of a predetermined impurity is low. When used as a coalesced raw material, the content of a predetermined impurity contained in the polymer or impurities resulting therefrom can be set low. Moreover, when the compound containing a sulfonic acid (salt) group and an amino group of the present invention is used as a raw material for a polymer for a water treatment agent, the polymer has a good calcium phosphate scale inhibiting ability. Therefore, the compound containing a sulfonic acid (salt) group and an amino group of the present invention can be preferably used as a raw material for additives such as a water treatment agent.

2 is a ¹ HNMR chart of a monomer containing a sulfonic acid (salt) group and an amino group obtained in Example 1. FIG.

Hereinafter, the present invention will be described in detail.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
[Compound of the present invention]
The compound containing a sulfonic acid (salt) group and an amino group of the present invention (hereinafter also referred to as “the compound of the present invention”) has a structure represented by the general formula (3).
In the general formula (3), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. Or represents a CH ₃ group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n is an average addition mole number of an oxyalkylene group, represents the number of 300, m represents the number of 0~10, _SO ³ - ^{M +} represents a sulfonic acid (salt) group (wherein, ^{M +} is a monovalent monatomic ions or multi with a positive charge Represents atomic ions).

In the general formula (3), and when _{R 2} is a single _{bond, H 2 C = C (R} 3) of the general formula (3) -R 2 in _{-O-, H 2 C = C (} R ₃ ) It means that it is represented by -O-. That _{H 2 C = C (R 3} ) -R 2 - is, _{R 3} is CH _3, methallyl group when _{R 2} is CH ₂ group, _{R 3} is CH _{3, R 2} is _CH 2 CH ₂ group Is an isoprenyl group, R ₃ is a CH ₃ group, R ₂ is a single bond, an isopropenyl group, R ₃ is a hydrogen atom, R ₂ is a CH ₂ group, an allyl group, R ₃ is a hydrogen atom, R _{3 When 2} is a CH ₂ CH ₂ group, it means a butenyl group, R ₃ is a hydrogen atom, and when R ₂ is a single bond, it means a vinyl group. R ₃ is particularly preferably a CH ₃ group because the polymerizability of the monomer represented by the general formula (3) is improved.

  N in the general formula (3) is an average addition mole number of the oxyalkylene group and is a number of 0 to 300. n may be appropriately selected depending on the use for which the compound represented by the general formula (3) is used. From the viewpoint of efficiently producing the compound represented by the general formula (3). , N is preferably 0 to 100, more preferably 1 to 50, and even more preferably 2 to 30 from the viewpoint of further improving the ability of the obtained copolymer to suppress the scale.

  M in the general formula (3) is preferably 0 or more and 5 or less, and more preferably 1 or more and 3 or less.

R ₁ in the general formula (3) is the same or different, and represents an alkylene group having 2 to 20 carbon atoms. However, since the compound represented by the general formula (3) has good polymerizability, an alkylene group having 2 to 4, based on the total amount of _{R 1,} preferably comprises 50 to 100 mol%, and more preferably contains 80 to 100 mol%, further preferably contains 90 to 100 mol%.
Specifically, the C2-C4 alkylene group is an ethylene group, a propylene group, or a butylene group. An ethylene group or a propylene group is particularly preferable. The alkylene group may be one type or two or more types. In the case of two or more kinds, the structure of —R ₁ —O— may be randomly continuous, alternately continuous, or continuously in blocks.

R ₄ in the general formula (3) represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, but the production yield of the compound represented by the general formula (3) Therefore, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 carbon atom is particularly preferable. The alkyl group may be linear or branched. In the alkyl group having 1 to 10 carbon atoms, part or all of the hydrogen atoms may be substituted with other functional groups, or may be unsubstituted. Examples of the functional group include a hydroxyl group, an alkoxy group, a sulfonic acid (salt) group, a carboxylic acid (salt) group, and an ester group.
Examples of the aryl group having 6 to 10 carbon atoms include a substituted or unsubstituted phenyl group. Examples of the substituent include a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid (salt) group, a carboxylic acid (salt) group, and an ester group.

In the general formula (3), the —SO ₃ ⁻ M ⁺ group represents a sulfonic acid (salt) group, and M ⁺ represents a monoatomic ion or polyatomic ion having a monovalent positive charge. Examples of the monoatomic ions include H ⁺ ; alkali metal ions such as Li ⁺ , Na ⁺ and K ⁺ , and transition metal ions such as Ag ⁺ and Cu ⁺ . Examples of polyatomic ions include H ₃ O ⁺ , NH ₄ ⁺ , and organic amine ions. The sulfonic acid (salt) group represents a sulfonic acid group or a sulfonic acid group, and the sulfonic acid group is a form in which M is H ⁺ .

  The polymer obtained by polymerizing the compound of the present invention has a structural unit derived from the compound of the present invention. The structural unit derived from the compound of the present invention is a structure in which the carbon-carbon double bond of the structural unit derived from the compound of the present invention is a single bond, and can be represented by the following general formula (5).

In the general formula (5), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. Or represents a CH ₃ group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n is an average addition mole number of an oxyalkylene group, 300 represents a number, m represents a number of 0 to 10, and SO ₃ ⁻ M ⁺ represents a sulfonic acid (salt) group (where M ⁺ represents a monoatomic ion or a polyvalent ion having a monovalent positive charge). Represents atomic ions).
[Production method of the present invention]
The production method of the present invention includes a step of reacting the compound represented by the general formula (1-1) or (1-2) with the compound represented by the general formula (4). Yes.
In the general formulas (1-1) and (1-2), R ₁ , R ₂ , R ₃ , and n are preferably in the form of R ₁ , R ₂ , R ₃ , and n in the general formula (3). Each of the embodiments and the preferred embodiments is the same.
X in the general formula (1-2) is a halogen atom, and examples thereof include a chlorine atom and a bromine atom.
The embodiments and preferred embodiments of R ₄ , M ⁺ and m in the general formula (4) are the same as the embodiments and preferred embodiments of R ₄ , M ⁺ and m in the general formula (3), respectively.
Specific examples of the compound represented by the general formula (4) include taurine, methyl taurine, ethyl taurine, n-butyl taurine, n-octyl taurine and salts thereof. Examples of the salt include metal salts, ammonium salts, and organic amine salts.

Reaction of the compound represented by the general formula (1-1) and the compound represented by the general formula (4) (hereinafter, the reaction is also referred to as “reaction I”, and the step of performing the reaction I is referred to as “step I ”) is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent.
Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, It is the range of 0.005-5 times mass normally with respect to the compound represented by General formula (1-1), Preferably 0.01-3 times mass is preferable. It is a range.

  The amount of the compound represented by the general formula (4) used in the step I is generally a molar ratio with respect to the compound represented by the general formula (1-1), and is generally represented by the general formula (1-1). ) / Compound represented by the general formula (4) = 2/1 to 1/2, preferably 1.7 / 1 to 1 / 1.7, more preferably 1.4. /1-1/1.4.

  The reaction of step I may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the compound represented by the general formula (1-1), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

  Reaction of the compound represented by the general formula (1-2) and the compound represented by the general formula (4) (hereinafter, the reaction is also referred to as “reaction II”, and the step of performing the reaction II is referred to as “step II ”) is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, It is the range of 0.005-5 times mass normally with respect to the compound represented by the said General formula (1-2), Preferably it is 0.01-3 times mass. Range.

  In the step II, the amount of the compound represented by the general formula (4) is used in a molar ratio with respect to the compound represented by the general formula (1-2). ) / Compound represented by the general formula (4) = 2/1 to 1/2, preferably 1.7 / 1 to 1 / 1.7, more preferably 1.4. /1-1/1.4.

  The reaction of step II may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the compound represented by the above general formula (1-2) as a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

  The reaction in Step II may be performed in a batch or continuously, and can be performed, for example, in either a tank-type reactor or a tubular reactor. After the reaction in Step II, a step such as desalting is preferably performed. The desalting step can be carried out by sedimentation separation, centrifugation, filtration, washing, etc., and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed. It is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in that a sufficient separation rate can be obtained.

The compounds represented by the general formulas (1-1) and (1-2) can be produced by a known method. For example, a method described in JP 2012-56911 A is preferably used.
For example, the compound represented by the general formula (1-1) includes (i) a method of reacting an alkylene oxide adduct of an unsaturated alcohol such as isoprenol with an alkali compound and epihalohydrin, and (ii) an unsaturated compound such as isoprenol. It can be produced by a method in which an alkali compound is reacted with a reaction product obtained by reacting an alkylene oxide adduct of alcohol with an epihalohydrin in the presence of a catalyst.

In the reaction (i), the alkali compound is not particularly limited, but alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred.
The amount of the alkali compound used in the reaction (i) is usually a molar ratio of alkylene oxide adduct of unsaturated alcohol / alkali compound = 15/1 to 1/15, preferably 5/1 to 1/1 /. 5, more preferably 3/1 to 1/3. You may use an alkaline compound in the state of aqueous solution. In this case, the reaction may be performed while removing water (including water produced as a by-product with the progress of the reaction).
The amount of the epihalohydrin used in the reaction (i) is usually a molar ratio of alkylene oxide adduct of unsaturated alcohol / epihalohydrin = 1/1 to 1/15, preferably 1/1 to 1/10. Yes, more preferably 1/1 to 1/5.
The reaction (i) is carried out in the presence of a phase transfer catalyst and / or a solvent, if necessary.

The catalyst used in the reaction of the alkylene oxide adduct of unsaturated alcohol and epihalohydrin in the method (ii) above (also referred to as “reaction (ii-1)”) may be either an acid or a base, but an acid is preferred. . The acid may be Lewis acid or Bronsted acid, but Lewis acid is preferred. As a Lewis acid, what is generally called a Lewis acid can be used. For example, boron trifluoride, tin tetrachloride, tin dichloride, zinc chloride, ferric chloride, aluminum chloride, titanium tetrachloride, magnesium chloride. And antimony pentachloride. The amount used is usually an alkylene oxide adduct of unsaturated alcohol / catalyst = 1 / 0.0001 to 1 / 0.1, preferably 1 / 0.0005 to 1 / 0.05, in molar ratio. Yes, more preferably 1 / 0.001 to 1 / 0.03.
The amount of epihalohydrin used in the reaction (ii-1) is usually a molar ratio, and is an alkylene oxide adduct of unsaturated alcohol / epihalohydrin = 1/1 to 1/30, preferably 1/1 to 1/10. Yes, more preferably 1/1 to 1/5.
Reaction (ii-1) is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but may be carried out in the presence of a solvent.

The alkali compound in the reaction of the reaction product (ii-1) and the alkali compound (also referred to as “reaction (ii-2)”) in the method (ii) is not particularly limited, but sodium hydroxide, Alkali metal hydroxides such as potassium hydroxide are preferred.
The amount of the alkali compound used in the reaction (ii-2) is usually a molar ratio, and the reactant / alkali compound of the reaction (ii-1) = 1/1 to 1/100, preferably 1/1. ˜1 / 50, more preferably 1/1 to 1/20. You may use an alkaline compound in the state of aqueous solution.
The reaction (ii-2) may be carried out in the presence of a solvent.
In addition, the reactant of the reaction (ii-1) is specifically a compound represented by the general formula (1-2). That is, the compound represented by the general formula (1-2) can be produced by the method of the reaction (ii-1).
The reaction temperature in the reactions (i), (ii-1), and (ii-2) is usually 0 to 200 ° C, preferably 15 to 150 ° C, more preferably 30 to 100 ° C. .
Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like.

As described above, the compound represented by the general formula (1-1) is, for example, the above (i),
Although it can manufacture by the method of (ii), when a catalyst is used at the time of manufacture, you may use for the manufacturing method of this invention with a catalyst remaining as it is.
The compound represented by the general formula (1-1) or (1-2) used in the production method of the present invention is subjected to steps such as desalting and removal of excess epihalohydrin, and then to Step I or Step II. It is preferable to use it. The desalting step can be carried out by sedimentation separation, centrifugation, filtration, washing or the like, and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed, and it is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in order to obtain a sufficient separation rate. Excess epihalohydrin can be easily removed by distillation, evaporation or the like. The above reactions (i), (ii-1), and (ii-2) may be carried out in batch or continuously. For example, the reaction may be carried out in either a tank-type reactor or a tubular reactor. it can.

The production method of the present invention essentially includes a step of reacting the compound represented by the general formula (1-1) or (1-2) with the compound represented by the general formula (4). These steps may be optionally included. Other steps include, for example, the step of concentrating or removing the reaction solvent when using a reaction solvent, the step of diluting with water and / or an organic solvent, the step of removing residual raw materials, and the case of using a reaction catalyst. Examples include a step of deactivating the reaction catalyst, a step of adding a polymerization inhibitor and a coloring inhibitor, and a step of adding an acid or alkali.

[Composition of the present invention]
The composition containing the compound of the present invention (hereinafter also referred to as “the composition of the present invention”) contains the compound represented by the general formula (3) as an essential component. The composition of the present invention may contain only the compound represented by the general formula (3), but may contain other components. The content of the compound represented by the general formula (3) in the composition of the present invention is preferably 10% by mass or more and 100% by mass or less with respect to 100% by mass of the composition of the present invention. More preferably, it is at least 99% by mass.

  The composition of the present invention may contain a polymerization inhibitor, and the content of the polymerization inhibitor is preferably 0 to 5000 ppm, more preferably 0 to 4000 ppm with respect to the composition of the present invention. preferable.

  The composition of the present invention preferably has a low content of the compound represented by the following general formula (6), and the content of the compound represented by the general formula (6) in the composition of the present invention is: It is preferably 0 mol% or more and 15 mol% or less, and preferably 0 mol% or more and 10 mol% or less with respect to 100 mol% of the compound represented by the general formula (3) contained in the composition of the present invention. Is more preferably 0 mol% or more and 8 mol% or less.

In the general formula (6), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. Or represents a CH ₃ group, and n is the average number of added moles of the oxyalkylene group, and represents a number of 0 to 300.

  The composition of the present invention may contain a solvent. As the solvent, water is preferable. The content of the solvent in the composition of the present invention is preferably 0% by mass or more and 90% by mass or less, and 0% by mass or more and 80% by mass or less with respect to 100% by mass of the composition of the present invention. It is more preferable.

In addition, the composition of the present invention may contain an alkali compound, a by-product other than the above, and the like.
The composition of the present invention is preferably produced by the production method of the present invention.

[Use of the compound (composition) of the present invention]
The compound (composition) of the present invention can be preferably used as a raw material for the polymer. That is, the compound of the present invention is preferably used as a monomer.
Since the compound (composition) of the present invention can be set to a low content of a non-polymerizable compound in which bisulfite is added to a double bond, when used as a polymer raw material, the polymer composition The content of the non-polymerizable compound contained in the product can be lowered.
Although the compound of this invention is good also as a raw material of a polymer independently, you may copolymerize with another monomer and may manufacture a polymer.
Examples of the other monomers include carboxyl group-containing monomers such as acrylic acid, maleic acid, and salts thereof; and sulfonic acid group-containing monomers such as (meth) allylsulfonic acid, styrenesulfonic acid, and salts thereof. ; Polyalkylene glycol chain-containing monomers such as alkylene oxide adducts of isoprenol and (meth) allyl alcohol; Amino group-containing monomers such as vinylpyridine; Amide monomers such as acrylamide and vinylpyrrolidone; Butyl acrylate And (meth) acrylic acid esters such as ethylhexyl acrylate; alkenes such as isobutylene and octene; vinyl carboxylates such as vinyl acetate; styrene, acrylonitrile, vinyl chloride and the like.
The polyalkylene glycol monomer composition of the present invention may be polymerized by any method. For example, a polymer can be produced by the method described in JP 2012-57095 A. In the polymerization, bisulfite can be used as a chain transfer agent, for example, but from the viewpoint of suppressing the generation of impurities during the polymerization reaction, persulfate, peroxide, organic peroxide, azo compound It is preferable to use together with the polymerization initiator selected from.
The polymerization ratio of the compound of the present invention and the other monomer is arbitrary, for example, a molar ratio of 100: 0 to 1:99, preferably a molar ratio of 60:40 to 1:99, 50: More preferably, it is 50-2: 98.
A polymer having a structural unit derived from the compound of the present invention (a structural unit represented by the above general formula (5)), a structural unit derived from the compound of the present invention and a structural unit derived from another monomer in moles. Polymers containing 100: 0 to 1:99 in a ratio, preferably 60:40 to 1:99, more preferably 50:50 to 2:98 are also included in the present invention.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
<Quantification of compound represented by general formula (1-1)>
The compound represented by the general formula (1-1) was quantified by liquid chromatography (hereinafter referred to as “LC”) under the following conditions.
Measuring device: 2695 manufactured by Waters
Column: Fortis (Type: Phenyl 5 μm, Size 4.6 mm ID × 150 mm)
Eluent: Pure water / acetonitrile = 5/5 (vol%)
Flow rate: 0.5 ml / min
Temperature: 40 ° C
Detector: UV (210 nm)
Sample preparation: 10 μl injection of 0.5% sample solution.

<Quantitative determination of the compound represented by the general formula (3)>
The yield of the compound represented by the general formula (6) and the conversion rate of the compound represented by the general formula (1-1) in the production of the compound represented by the following general formula (3) are as follows by LC. It quantified on condition of this.
Measuring device: Hitachi High-Technologies
Column: CAPCELL PAK C8DD (5 μm, Size 4.6 mm ID × 250 mm) manufactured by Shiseido Co., Ltd.
Eluent: 10 mM sodium phosphate (pH 6.8) / acetonitrile = 55/45 (vol%)
Flow rate: 1 mL / min
Temperature: 40.0 ° C
Detector: RI
Sample preparation: 10 μl injection of 1% sample solution.
The amount of the compound represented by the following general formula (3) is (amount of the compound represented by the general formula (1-1)) × (conversion rate of the compound represented by the general formula (1-1)). )-(Production amount of the compound represented by the general formula (6)).

<Confirmation of compound represented by general formula (3)>
The sample was dissolved in heavy water, and the production of the compound represented by the general formula (3) was confirmed by ¹ HNMR.
¹ HNMR measurement conditions:
Measuring device: “Unity Plus” 400 MHz manufactured by Varian
¹ HNMR (single pulse), pulse angle 45 °, pulse repetition time 3 seconds, integration 16 times.

<Quantification of sodium 3-allyloxy-2-hydroxy-1-propanesulfonate in polymer aqueous solution>
It carried out using the liquid chromatography on the following conditions.
Device: e2695 manufactured by Waters
Detector: UV detector 2489 manufactured by Waters
Column: Shodex RSpak DE-413L manufactured by Showa Denko KK
Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Mobile phase: 0.1% aqueous phosphoric acid solution.

<Quantification of monomer represented by general formula (3) in aqueous polymer solution>
Measuring device: Tosoh Corporation 8020 series
Column: CAPCELL PAK C1 UG120 x 2 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 0.01M sodium dihydrogen phosphate aqueous solution / acetonitrile = 49/51 (mass ratio) pH 7
Flow rate: 1.0 mL / min.
Detector: RI.

<Measurement of weight average molecular weight of polymer>
Device: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 mL / min.
Calibration curve: Polyacrylic acid standard made by Soka
Eluent: 0.1 M sodium acetate aqueous solution / acetonitrile = 75/25 (mass ratio)
<Measurement of solid content>
The polymer (composition) was left to dry for 2 hours in an oven heated to 120 ° C. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

<Scale inhibition rate of calcium phosphate>
Deionized water, boric acid-sodium borate pH buffer solution, aqueous calcium chloride solution, aqueous polymer solution obtained in Examples and Comparative Examples, and aqueous sodium phosphate solution were added in this order to a 225 ml screw cap bottle, pH = 8 .6, 100 ml of a test solution having a polymer concentration of 7 mg / L in terms of solid content, calcium hardness = 150 mgCaCO ₃ / L, phosphate ion = 10 mgPO43− / L was prepared. After sealing, it was allowed to stand at 60 ° C. for 24 hours. The test solution was filtered through a filter paper having a pore size of 0.1 μm, and the residual phosphate ion concentration in the filtrate was analyzed.
A blank test solution obtained by removing the polymer from the above test solution was prepared as a blank, and the same operation was performed to analyze the residual phosphate ion concentration. The calcium phosphate scale inhibition rate was determined by the following formula.
Calcium phosphate scale inhibition rate = 100 × (R−Q) / (P−Q)
P: Charged phosphate ion concentration (mg / L)
Q: Blank residual phosphate ion concentration (mg / L)
R: Residual phosphate ion concentration (mg / L).

<Synthesis Example of Compound Represented by General Formula (1-1)>
In a 1 L four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube, 347.4 g of an ethylene oxide average 10-mole adduct of isoprenol (hereinafter also referred to as “IPN10”, hydroxyl value 106.5 (mgKOH / g)), Epichlorohydrin (338.4 g) and 48% NaOH (82.2 g) were charged, and the mixture was allowed to react by stirring for 6 hours while maintaining the temperature at 50 ° C. After the reaction, the generated salt is removed, and then the epichlorohydrin and water are removed from the remaining organic layer to obtain intermediate (A) (in the above general formula (1-1), n is an average of 10 and R ₁ is 355.8 g of a reaction solution containing a compound having a structure in which CH ₂ CH ₂ group, R ₂ is CH ₂ CH ₂ group, and R ₃ is CH ₃ group (hereinafter referred to as “IPEG10”) was obtained. As a result of analysis by liquid chromatography, 293.4 g of intermediate (A) and 21.6 g of IPN10 were contained.

<Example 1>
Into a 1 L four-necked flask equipped with a stirring blade, thermometer, condenser, and dropping funnel, the reaction solution was charged so that the intermediate (A) was 288.9 g, and the temperature was increased to 50 ° C. while stirring. Warm up. A mixture of 159.3 g of 65% N-methyl taurine aqueous solution and 47.6 g of pure water was slowly added dropwise over 1 hour while maintaining the internal temperature of 50 ° C., and the mixture was further stirred for 5 hours. An inventive composition (1) was obtained. The composition (1) of the present invention was evaluated by ¹ HNMR and liquid chromatography, and the target compound (in the general formula (3), R ₁ was a CH ₂ CH ₂ group, R ₂ was a CH ₂ CH ₂ group, R ₃ is a CH ₃ group, R ₄ is a CH ₃ group, n is 10 on average, m is 1 and the formation of the compound (hereinafter referred to as “IPET10”) was confirmed.
The generation of no carbon-carbon double bond than ¹ HNMR by-product was not observed (0%). The conversion of IPEG10 was 100% by liquid chromatography.
The composition of the composition (1) of the present invention is summarized in Table 1.

<Example 2>
A 300 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 63.5 g of pure water and 0.9 g of a 0.6% Mole salt aqueous solution and heated to 87 ° C. while stirring. did. Next, 45.0 g (0.5 mol) of 80% acrylic acid aqueous solution (hereinafter also referred to as “80% AA”) and 40% 3-allyloxy-2-hydroxy-1-propanesulfonic acid with stirring. The composition (1) of the present invention was adjusted so that 29.9 g (0.055 mol) of an aqueous sodium solution (hereinafter also referred to as “40% HAPS”) and 41.1 g (0.055 mol) of IPET10 were obtained. 32.5 g of 15% sodium hydrogensulfate aqueous solution (hereinafter also referred to as “15% NaPS”) and 20.9 g of 35% sodium hydrogensulfite aqueous solution (hereinafter also referred to as “35% SBS”) It dripped from the nozzle. Each solution started dripping simultaneously. The dropping time of each solution is 180 minutes for 80% AA, 130 minutes for 40% HAPS, 150 minutes for the composition (1) of the present invention, and 14.2 g for the 15% NaPS for the first 120 minutes, 18.3 g. For a total of 190 minutes and 35% SBS for 170 minutes. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was kept (aged) at 87 ° C. for 30 minutes to complete the polymerization. In this way, an aqueous solution of the polymer (1) was obtained. The weight average molecular weight of the polymer (1) was 7000.

<Comparative Example 1>
In Example 1, the amount of pure water charged was 41.7 g, the dripping amount of 80% AA was 75.1 g (0.83 mol), and the dripping amount of 40% HAPS was 99.8 g (0.18 mol). In addition, the addition time of 40% HAPS was 24.9 g in 20 minutes and then 74.8 g in 120 minutes for a total of 140 minutes, the addition amount of 15% NaPS was 27.1 g, and the addition time of 15% NaPS was 130 minutes. Example 1 except that the amount of dripping 35% SBS was changed to 11.6 g, and the composition (1) of the present invention was not used. In the same manner as in Example 1, an aqueous solution of the comparative polymer (1) was obtained.

<Comparative example 2>
In Example 1, the dripping amount of 80% AA was 54.0 g (0.6 mol), the dripping amount of 40% HAPS was 35.9 g (0.066 mol), and the dripping time of 40% HAPS was 15 minutes. 9 g, then 26.9 g in 115 minutes for a total of 130 minutes, the drop amount of 15% NaPS was 39.0 g, the drop time of 15% NaPS was 17.1 g for 120 minutes, and then 22.0 g for 70 minutes. In 190 minutes, the dripping amount of 35% SBS was changed to 25.1 g, and 34.7 g (0.066 mol) of IPN10 was used without using the composition (1) of the present invention. An aqueous solution of the comparative polymer (2) was obtained in the same manner as in Example 1 except that the dropping time of was set to 170 minutes.

<Example 3>
For the polymer (1) and the comparative polymers (1) and (2), the scale inhibition rate (%) of calcium phosphate was measured according to the above method. The results are summarized in Table 2.

As is clear from Table 2, the polymer using the compound of the present invention as a raw material has better calcium phosphate scale inhibiting ability as compared with conventional polymers. Therefore, it was revealed that the monomer of the present invention can be preferably used as a raw material for these polymers.

Claims (3)

A compound represented by the following general formula (3).

In the general formula (3), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. or an CH ₃ group, _{R 4} represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, n is an average addition mole number of the oxyalkylene group, 1 50 represents a number, m represents a number of 0 to 10, and SO ₃ ⁻ M ⁺ represents a sulfonic acid (salt) group (where M ⁺ represents a monoatomic ion or a polyvalent ion having a monovalent positive charge). Represents atomic ions). A sulfonic acid (salt) group and an amino group, comprising a step of reacting a compound represented by the following general formula (1-1) or (1-2) with a compound represented by the following general formula (4): The manufacturing method of the compound containing this.

In the general formulas (1-1) and (1-2), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, and R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group, or a single bond. R ₃ represents a hydrogen atom or a CH ₃ group, and n represents the average number of added moles of the oxyalkylene group, and represents a number of 1 to 50 . In general formula (1-2), X represents a halogen atom.

In General Formula (4), R ₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, m represents a number from 0 to 10, and SO ₃ ⁻ M ⁺ represents Represents a sulfonic acid (salt) group (where M ⁺ represents a monoatomic ion or polyatomic ion having a monovalent positive charge). The polymer containing the structural unit represented by following General formula (5).

In the general formula (5), R ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, R ₂ represents a CH ₂ CH ₂ group, a CH ₂ group or a single bond, and R ₃ represents a hydrogen atom. or an CH ₃ group, _{R 4} represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, n is an average addition mole number of the oxyalkylene group, 1 50 represents a number, m represents a number of 0 to 10, and SO ₃ ⁻ M ⁺ represents a sulfonic acid (salt) group (where M ⁺ represents a monoatomic ion or a polyvalent ion having a monovalent positive charge). Represents atomic ions).

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